Coating composition comprising a vehicle containing drying oil-modified alkyd or phenol-formaldehyde resin, pigment, litharge, and calcium hydrate



- Patented July 29, 1947' UNITED srA'rss COATING COMPOSITION mom: CONTAINING ALKYD o PATENT orrics OMPBISING A VE- D YING OIL-MODI- PHENOL-FOBMALDE- FIED HYDE RESIN, PIGMENT, LITHARGE, AND

CALCIUM HYDBATE Ladislaus Balassa,

E. L du Pont de Nemours Swarthmore, Pa... assignor to & Company Wilming ton, Del. a. corporation oi-Delaware No Drawing.

extensively in the decorative and protective coating industry for some time. Such compositions are applied as the first coating to the surface to be protected to form a base tor subsequent socalled finishing coatings. The primer compositions are ordinarily characterized by relatively high pigment content in a non-volatile film forming vehiclewhich may be of a resinous or oleoresinous type. The compositions may be of the air drying or of the baking type. For many uses they may desirably possess anti-corrosive -(or metal protective) properties. Such properties are imparted to the compositions by the type of pigment used. Desirable and substantially requisite properties of primer compositions are that films or coatings produced therefrom possess good water resistance and that the coatings applied to the substrate dry rapidly, particularly the airdrying types. This latter requisite is of particular importance where speed of production in finishing articles is necessary. While considerable progress has been made in the improvement of such primer compositions much is still to be desired in the speed of drying of the coatings and m the water resistance of films produced so porcelain lined ban mm with steel bans and therefrom.

This invention presents as the principal object the provision of improved primer coating compositions,

Another object is the provision of such primer.

coating compositions possessing rapid drying properties and becoming free from top tack within a relatively short period of time after application.

Still another object is the provision of primer coating compositions possessing improved water resistance overknown available comparable compositions. T

A further object is the provision of means for preparing such compositions which are simple and economical.

Application January 25, 1944, Serial No. 519,653

7 6Claims. (01. 260-19) Other objects will be apparent as the description of the invention proceeds.

These objects are accomplished in-the present invention by the addition 0! definitely proportioned minor quantities of litharge'and calcium I hydrate durlng the dispersion of the pigment in the film forming vehicle of the composition.

The invention will be more clearly understood from the following examples in which the parts are by weight. w

l EXAMPLE I Zinc chi-mate primercomposition Zinc chromate base: Parts China-wood oil-phenol/forma1dehyde resin varnish Zinc yellow pigment.. 52.8 Litharge .4 Calcium hydrate.. .4 Xylene 14.9

The China-wood oil-phenolic resin varnish is a 123/ gallon oil length varnish having a viscosity of A (Gardner-Holdt scale) and'total solids of 35.0%, the solvent or thinner being a high solvency petroleum naphtha. T

The ingredients were charged into a stone or turned for approximately 50,000 cycles. The preferred ball to batch ratio by weight.

Asbestine base:

China-wood oil-phenol/formaldehyde Parts resin varnish 34.;6'

- Asbestine (magnesium silicate) 35.6 Xylene 29.8

The China-wood oil-phenolic resin varnish used was asdescribed above.

The ingredients were charged into a porcelain or porcelain lined pebble mill with pebbles and the mill and contents then turned for approxiis approximately 3:1

matel'y 50,000 cycles. Porcelain balls may be used in place of pebbles and the preferred pebble or ball to batch ratio is 2:1.

Finished p imer: I Parts Zinc chromate bas a s 50.6 Asbestine base 16.2 Phenolic resin varnish 22.4 Ethyl cellulose solution 8.6 Xylene 2.2

The phenolic resin varnish is a 12 /2 gallon oil 7 length China-wood oil-oil soluble phenol-formaldehyde varnish thinned with xylene to approximately .'l5% solidsand having a viscosity of 2-4 (Gardner-Holdt scale).

The ethyl cellulose solution used wasan approximately 22.5% solution of 20 centipoise ethyl cellulose in a solvent mixture of 4 parts xylene to 1 part ethyl acetate (85-88%).

The finished primer was prepared by mixing the ingredients in a suitable mixing tank, prefment shows considerable top-tack even after 30 minutes drying at room temperature.

A conventional test for the quantitative determination of top-tack may be carried. out as follows. Two suitably solvent cleaned panels, 4 inches by 12 inches, are sprayed on one face. with the primer composition to be tested and are then allowed to dry at room temperature (70-90 F.) for minutes. The primed panels are then placed face to face and the two panels placed under a 30 pound weight and allowed to remain so for 24 hours. The weight should be applied over the entire area of the panels. After 24 hours the panels are separated. The top-tack 4 The drying oil modified alkyd resin used was a 49% China-wood/linseed oil (1:1) modified glyceryl phthalate solution in xylene with a total solids content of 60%.

The ingredients were charged into a ball mill and the pigment dispersed in the film forming resin as described under Example I.

Asbestine base: Parts Drying oil modified alkyd resin solution 19.2 Xylene Q. 34.6 Asbestine (magnesium silicate) 46.2

The alkyd resin solution used was the same as used in dispersing the zinc chromate pigment above.

Finished primer composition: Parts Zinc chromate base 44.0 Asbestine base 10.3 China-wood/linseed oil modified alkyd resin solution 36.4 Ethyl cellulose solution 9.3

The alkyd resin solution and ethyl cellulose solution used were those as previously described.

The finished composition maybe prepared according to the procedure described under Example I or by any other suitable or convenient means.

The litharge and calcium hydrate content in the finished primer, based on t e film forming Vehicle is 0.74% for each.

is considered to be in direct ratio to the efiort Y necessary to separate the panels and to the percentage area of bare metal showing due to the greater cohesion of the primer composition films than to the adhesion of the primer film to the metal substrate. The primer composition of the present example when tested according to such a procedure showed only 2% bare metal as against approximately 15% bare metal with a similar composition in which no litharge and calcium hydrate was used in dispersing the pigment.

Exanrra II Zine chromate primer composition Zinc chromate base: Parts Drying oil modified alkyd resin solution 6.8 Xylene -a 31.7 Zinc chromate pigment 60.6 Calcium hydrate .45 Litharge .45

, Parts Mill base Q 60.0

Alkyd resin solution 35.0 Xylene 4.6 Cobalt naphthenate drier .2 Manganese naphthenate drier .2

When applied to suitably prepared metal substrate by spraying in film builds up to .0005 inch 4 the primer composition dries essentially tack-free within ten minutes. A similar product in which litharge and calcium hydrate are not present during the pigment dispersion operation retains considerable top tack after several hours drying. In the test described under Example-I the composition of this example showed only 1% bare metal while the control composition showed more than 15%.

ExAurLn In Dark grey primer Mill base: Parts Alkyd resin solution 8.0 Xylene 32.0 Titanium dioxide 10.0 Powdered slate 37.4 Talc 6.0 Absentine 6.0

Calcium hydrate .2 Litharge .4

The ingredients were charged into a ball mill and the pigments and fillers dispersed in the film forming resin by turning for approximately 50,000

cycles with a hall to batch ratio of approximately 3:1 by weight.

Finished primer composition:

Y The above ingredients are thoroughly mixed as described imder Example II or by any other suitable or convenient means. to'obtain a homogeneous composition.

'me alkyd resin solution used in this composipreferred in the so-called harder film forming vehicles while in the softer vehicles more calcium tion was a 43% dehydrated castor oil modified glyceryl phtha1ate-50% solution in Iii-flash naphtha.

The litharge and calcium hydrate content in the finished primer composition is 1.2% and 0.6%

respectively based on the total binder or film forming solids.

This primer composition when used as desoribed under the previous examples yieldsre suits as to improve top tack and decreased drying time of the same order as obtained with the chromate primers. The composition may be applied ito substrates other than metal and such use will be appment to those skilled in the of using primer compositions.

cipal use as metal protective primers, wood.

art-

. positions.

hydrate and less litharge will be preferred. In

carrying out the invention it is essential that.

the litharge and calcium hydrate be added duringthe dispersion operation.- These materials cannot be merely added to the finished coating compositions as then they would not produce the It is also to be understood that litharge or calcium hydrate alone are inefiective,

desired result.

and that both must be present.

The compositions described herein are of prinprlmers and other relatively highly pigmented paint compositions in which rapid dry and reduced top tack is desirable or necessary. Various uses will be readily apparent to-those skilled in the art of protective and decorative coating com- It will be seen irom the above description that a marked advance has been made in the art in providing coating compositions which possess as principal advantages over similar compositions now available, increased speed of drying, reduced top tacksoffllms prepared therefrom, improved moisture resistance and harder coatings. Other The ingredients are charged into a suitable ball mill and the pigments dispersed'as described under mample l'II.

Finished primer composition: Parts m base 60.0

011 modified alkyd resin solution 31.8 Xylene 7.8 Cobalt naphthenate drier J2 Manganese naphthenate drier .2

advantages will be readily apparent through the use of the compositions. I

It is apparent that many widely different embodiments of this invention may be made without departing from the spirit and scope thereof, and therefore, it is not intended to be limited except as indicated in the appended claims.

I claim:

1. A pigmented coating composition a film of which of about .0005 inch in, thickness dries at room temperatures in less than about '10 minutes to a tack-free stage, comprising a vehicle containing a resin selected from the group consisting of alkyd and phenol formaldehyde resins modified with a drying fatty 011, a. pigment and from .1% to 4.0% of litharge and calcium hydrate based on the total film-forming solids, the ratio of litharge to calcium hydrate being between 4 parts of litharge to 1 part of calcium hydrate and 1 part of litharge to 4 parts of calcium hydrate,

.The ingredients are mixed as previously de-' scribed to obtain a homogeneous composition.

The alkyd resinused in this example was a 50% soya bean oil'modified glyceryl phthalate 5 resin-% solution in a solvent mixture of mineral spirits 2 parts and high solvency petroleum naphtha 1 part.

when used as previously described the primer composition yields results as to improved top tack and decreased drying time of the same order as obtained with the chromate primers.

The litharge and calcium hydrate content in the finished primer is 1.2% and 1.8% respectively based on the total binder or film forming solids.

Other film forming vehicles than those shown in the examples may be used, those based on drying fatty oils being in general preferred.

It has been found that the combined litharge and calcium hydrate in the finished composition may vary between 0.1% and 4.0% based on the film forming solids with a preferred range of 0.25 to 3.0%. While the litharge and the calcium hydrate are preferably used in substantially equal amounts they may be used in ratios as widely varied as 80:20 or 20:80. The particularratio used will be governed largely by particular properties desired in the finished product. In general more litharge and less calcium hydrate is the said pigment having been dispersed in the said vehicle in the presence of the said litharge and calcium hydrate.

2. The composition of claim 1 in which the litharge and calcium hydrate are present in equal amounts and their combined weight is from .25 to 3.0% of the film-forming solids.

3. The process of preparing protective pigmented coating compositions a him of which having a. thickness of .0005 inch dries at room temperatures to a tack-free stage in less than about 10 minutes which comprises dispersing a pigment in a vehicle containing a resin selected {mm the group consisting of alkyd and phenol formaldee hyde resins modified with a drying fatty oil and during the dispersion adding from .1'% to 4.0% of litharge and calcium hydrate based on the total film-forming solids, the ratio of litharge to calcium hydrate being between 4parts of litharge to 1 part of calcium hydrate and 1 part of litharge to 4 parts of calcium hydrate.

4. The process of claim 3 in which the litharge and. calcium hydrate are present in equal amounts and their combined weight isfrom .25 to 3.0% of the film-forming solids.

5. A metallic surface having a protective coating thereon of the composition of claim 1.

6. The'pr'ocess of preparing a priming composition which is highly resistant to corrosion and a film of which .0005 inch in thickness dries to the REFERENCES CITED tack-free stage in less than about 10 minutes i which comprises charging a ball mill with a ve- 2; i gm fare record m the hicle containing a. resin selected from the group consisting of alkyd and phenol formaldehyde Q UNITED STATES PATENTS resins modified with a drying fatty oil, a pigment N and a solvent, dispersing the pigment in the veg??? g hide by gmdmg the said 11mm, and during 2 308 498 Earhart et a1 11: Jan. 19 1943 the grinding cycle adding thereto .4%'0f litharge and .4% of calcium hydrate based on the entire 10 OTHER E ER NCES Pages 502 and 503, Protective and Decorative LADISLAUS S Coatings, by Mattiello, vol. 1, 1941. 

